Capillary active compounds and process of preparing them



Patented Mar. 9, 1943 CAPILLARY ACTIVE COMPOUNDS AND raocnss or PREPARING THEM Ludwig Orthner, Carl Platz and Hans Keller, Frankfort-on-the-Main, and Heinz Siinke, Bad Soden in Taunus, Germany; assignors, by mesne assignments, to General Aniline & Film Corporation, New York, N. Y., a corporation of Dela:

ware

N 0 Drawing.

Application January 14, 1939, Se-

rial No. 250,925. In Germany January 1'1, 1938 4 Claims.

The present invention relates to capillary active compounds and to a process of preparing them.

We have found that agents of high capillaryv wherein R and R1 represent aliphatic hydrocarbon radicals of high molecular weight, Ra stands for hydrogen or an organic radical, R and R1 may, for instance, be aliphatic hydrocarbon radicals having at least 3 carbon atoms, and R1 and R2 together containing at least 11 carbon atoms. Especially suitable are also amines wherein R and R1 contain 8 or more carbon atoms and further amines wherein R contains 12 to 18 carbon atoms, R1 2 to? carbon atoms and R2 contains either 2 to 4 carbon atoms or represents hydrogen. Such amines are, for instance: cli-(n-hexyl) amine, dilsohexylamine, di-alpha-ethylhexyL amine, di-octylamine, butyldodecylamine, didodecylamine, di-octodecylamine, methyl-dihexylamine, diisoheptyl-hydroxyethyl-amine, diheptyl-benzylamine. Such secondary amines may be obtained by known methods from carboxylic acids or mixtures of carboxylic acids, for instance, by transforming these acids into the nitriles and hydrogenating the nitriles thus obtained. Primary amines which are simultaneously formed are separated by distillation. Suitable carboxylic acids are, for instance, caproic acid, caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, oleic acid, ricinolic acid, alphaethylhexylic acid. The amines may be used as such or in admixture with one another. The parent materials may also be prepared from commercial mixtures of carboxylic acids. It is, for instance, possible to transform into amines, by way of nitriles, the carboxylic acid mixtures formed in the oxidation of paraflin or of mineral oils. There are further suitable the mixtures of carboxylic acids which are obtained by treating with alkali the alcohols of high molecular weight formed in the catalytic hydrogenation of carbon oxides. Parent materials suitable for the preparation of amines are also carboxylic acids or mixtures of carboxylic acids which are obtained by treating carbon monoxide or carbon dioxide, in the presence of an alefine and perhaps of hydrogen, with steam or by causing a halogenated hydrocarbon to react with potassium cyanide and saponifying the product obtained.

The amines may also be obtained by other known methods, for instance, by causing suitable halogenated hydrocarbons to react with ammonia or amines.

Hydrophilic groups are introduced into these amines by known methods. The amines may be rendered soluble in water by treating them with a poly-basic inorganic acid or its anhydride or a chloride thereof, such as sulfuric acid, fuming sulfuric acid, sulfuric anhydride, chlorosulfonic acid, potassium chlorosulfonate, sodium fluorosulfonate, aminosulfonic acid, phosphoric acid, phosphoric anhydride, phosphorous anhydride, boric acid, boric anhydride, In case the amines contain hydroxyl groups, they may be made watersoluble, for instance, by treating them with sulfuric acid, chlorosulfonic acid or fuming sulfuric acid, sulfuric acid esters being thus formed. If the amines contain double bonds, addition products are formed by the action of the sulfonating agents, whereas in the presence ofaromatic nuclei aromatic sulfonic acids are mainly formed. If the amines are free from OH-gr'oups, double bonds and aromatic nuclei, they may be made soluble in water by treating them, in the presence of pyridine, with chlorosulfonic acid or sulfuric anhydride; sulfamic acids are thus obtained. When phosphorus chlorides are used, such as phosphorus pentachloride, phosphorus oxy-chloride, phosphorus trichloride, the solubility in water is obtained in the following way: some of the chlorine atoms react with the amines hydrogen chloride being evolved and the remaining chlorine atoms are hydrolyzed, in a second reaction, or, in case hydroxyl groups are present in the molecules, chlorides of phosphoric acid esters are formed which are, thereupon, saponified to form the corresponding acid phosphoric acid esters. The presence of a diluent, is of advantage, such as dimethyl ether, diethyl ether, beta. beta'-dichlorodiethyl ether, dichloro-methane, dichlor-ethane, carbon tetrachloride, sulfur dioxide, further the presence of a tertiary base, such as pyridine, .dimethylaniline. The sulfonic acid group may, however, also be introduced in an indirect manner by treating the amines with for instance chlorethanesulfonic acid, bromethanesulfonic acid, benzyl-chloride sulfonic acid, chlorohydroxypropane-sulfonic acid, beta-chloropropanedisulfonic acid, chloracetonesulfonic acid. The sulfonic acid group may, furthermore, be introduced by condensing the amines with aldehydeor ketone-sulfonic acids, for instance acetaldehyde-disulfonic acid, acetone monoand disulfonic acid, benzaldehyde-sulfonic acids and subsequently hydrogenating the products obtained. Theamino-alkyl-sulfonic acids thus obtained may then also be transformed into sulfobetaines by treating them with, for instance, methyl chloride, ethyl bromide, dimethyi-sulfate, ethylene oxide, :benzyl chloride, sodium butyl sulfate.

The amines may further be rendered soluble in water or in alkali by causing them to react with poly-basic carboxylic acids. Such acids are, for instance, oxalic acid, succinic acid, maleic acid, diglycolic acid, thiodiglycolic acid, dithiodiglycolic acid, phthalic acid, sulfophthalic acid, sul- Iosuccinic acid. The amines may also be caused to react with the anhydrides, esters or chlorides of such acids.

A further method for rendering the products soluble in water consists in causing the amines to react with halogenated carboxylic acids, salts, esters or amides thereof, such as monochloracetic acid, monochloracetic acid methyl-ester, chloracetamide, beta-chloropropionic acid, bromosuccinic acid and transforming, if desired, the products obtained into betaines, for instance, by treating them with methyl chloride, ethyl bromide, dimethyl sulfate, ethylene oxide, benzyl chloride, sodium butyl sulfate, to improve the fastness of the products to lime, alkali and acids.

The compounds containing amlnoor iminogroups may, furthermore, be made water-soluble by transforming them into quaternary ammonium bases by treating them, for instance, with methyl chloride, ethyl bromide, dimethyl sulfate, diethyl sulfate, benzyl chloride.

A further possibility of making the amines soluble in water consists in causing them, preferably in the presence of a catalyst, such as an alkali metal, an alkali metal oxide, to react at raised temperature, with alkylene oxides or the corresponding chlorhydrins, especially ethylene oxide, monochlorhydrins, mixtures of ethylene oxide with propylene oxide, or with glycide, epichlorhydrin, glycerol chlorhydrin. Further solubilizing groups may be introduced into the reaction products thus obtained, by treating them with polybasic inorganic acids, by causing them to react with halogen-sulfonic or -carboxylic acids or by means of polycarboxylic acid anhydrides.

A further method Of rendering the products water-soluble consists in transforming the amines, by means of phosgene, into isocyanates or carbamic acid chlorides and then condensing these products with amino-acids, such as sarcosine, methyl-taurine, with albumin decomposition products or with amino-poly-hydroxy-compounds such as methylglucamine or hydroxysulfonic acids, such as hydroxy-ethane-sulfonic acid.

The following products may, for instance, be obtained by the process of the present invention:

(1) Dodecyl-hexyl-phthalic acid semi-amide:

COOII (2) Di-octylsulfamic acid:

(a) Di-isoheptyl-benzylafminosulfonic acid:

C1HutIiI-C1Hxs (IJHI (4) Di-alpha-ethylhexyl hydroxyethylaminesulfuric acid ester:

The products obtained by the process of the invention have capillary active properties and may be used for treating materials or various kind, such as textiles, leather, paper and the like. They display a high wetting and emulsifying action; they may also be used with advantage as levelling and penetrative dyeing agents. Some of the products have a washing power or may be used as softening agents. The wetting effect, even in mercerizing liquors, is especially high with compounds in which the radicals R1 and R2 contain branched chains. The products may be used as such, in admixture with one another or with other capillary active substances, such as soap and other textile adjuvants, with colloidal substances such as mucilage, glue, water-soluble cellulose derivatives, starch, bentonite or the like or with or anic solvents, such as butanol, xylenyl-glycol; but also with inorganic salts, such as Glaubers salt, sodium carbonate, sodium pyrophosphate, trisodium phosphate, sodium metaphosphate or with agents yielding oxygen such as sodium perborate or so- 1 ed, while stirring, to 241 parts of butyldodecylamine boiling at 150 C. to 152 C., at a pressure of 3 mm.; the temperature rises spontaneously to 60 C. to 70 C. The mixture is further stirred, for half an hour, at 65 C. to 70 C., cooled to 15 C. to 25 C., and about parts of a caustic soda solution of 37 per cent strength are then added. The product must necessarily have, in an aqueous solution, an alkaline reaction to phenolphthalein. It then dissolves in water to a clear solution having a strong foaming action and a high wetting effect.

Instead of the dodecylbutyl-amine there may be used an amine obtainable in the followin! manner:

A middle oil formed in the catalytic hydrogenation of coal under high pressure, is chlorl nated in such a way that monochloro-derivatives are, for the main part, formed. By causing the product to react with n-butylamine and purifying by way of the hydrochloride the products formed, an amine-fraction is obtained which under a pressure of 3.5 mm., passes over at a ter5nperature comprised between 126 C. and 14 C. i

This amine-mixture yields when caused to react with di'glycolic anhydride a washing agent and fulling agent free from fat.

(2) 16 parts of monochloracetic acid are added to 83 parts of a mixture of secondary amines (amine number 245), which is prepared from the carboxylic acids containing '7 to 9 carbon atoms, obtained by the oxidation of paraflin, by transformation into nitriles and reduction of the nitriles to secondary amines, whereby primary amines are separated. The mixture is heated for 20 hours at 110 C. to 120 C., while stirring in a short reflux apparatus. 80 parts of a caustic soda solution of 40 per cent strength are then added and the product is distilled with superheated steam until a test portion of the residue freed from the caustic soda solution dissolves in water to a clear solution. The residue is then introduced in a separating apparatus, the alkaline lower layer is removed and hydrochloric acid is added to the upper layer, which is then washed several times with water, redissolved in caustic soda solution and made up with water to 300 parts. A product is obtained which may advantageously be used as wetting agent, even in alkaline liquors.

(3) 19 parts of bromacetic acid ethyl ester are added to 321 parts of n-tetradecyl-di-nbutylamine and the whole is stirred for 1 hour at 80 C. to 90 C. under reflux. A product is obtained which dissolves in water to a clear solution which by treatment with caustic soda solution is transformed into a body of the followin constitution:

This product may be used as washing agent for wool also in water containing a large quantity of lime. A product of similar properties is obtained by using instead of the above amine a technical aminein which the tetradecyl radical is exchanged for hydrocarbon radicals contained in palm nut oil.

(4) 9.4 parts of monochloracetic acid are added to 50 parts of di-n-octylamine and the whole is heated under reflux for 20 hours at 110 C. to 120 C., while stirring. A solution of 6 parts of caustic potash in 12 parts of water is added and the amine in excess is removed by steam distillation. The reaction product is acidified by means of dilute hydrochloric acid until Congopaper assumes a distinct blue colouration, the acid is neutralised by means of sodium acetate and the whole is agitated with ether. The ethereal residue has the following constitution In'the form of an alkaline salt it may be used as wetting agent. The properties of the product may be enhanced by a treatment with bromomethyl, a product having a betaine-like constitution being thus obtained.

19 parts of bromacetic acid ethyl ester are added to 38 parts of n-octodecyl-di-n-butyiamine (boiling under a pressure of 3.5 mm. mercury at 219 C. to 222 C.) and the whole is 'stirred at 80 C. to 90 C. under reflux. A product is obtained which dissolves in water to a clear solution and has the followimg constitution:

('nHg'l-N-Cdia Br CHzCOOCrHs which may be transformed into the amide by treatment with ammonia and may be saponified by treatment with caustic potash solution. The betaine thus obtained is a very good washing agent for white goods.

(6) 25 parts of di-(alpha-ethylhexyl)-amine and 10 parts 01 pulverized succlnic anhydride are heated at C. to C. for 1 hour, while stirring, and when dissolution has occurred the temperature of the mixture is raised for a short time to C. to C. The tough honey-yellow reaction product is made into a paste of 50 per cent strength with a solution of 5.6 parts of caustic potash. The product yields in water strongly foaming clear solution having capillary active properties. The product has the following constitution:

cm. om)i.cmcntncntcmcnzncm CIHI CzHs 0.CH:.CH:.C 0 0K (7) 0.3 part of sodium methylate is added to,

32.5 parts of n-butyloctadecylamine and at 150 C. to C. ethylene oxide is introduced until 50 parts are adsorbed. The product dissolves in water to a clear solution and may be used as washing agent.

By treating 32.5 parts of the above amine with 35 parts of ethylene oxide and adding in the course of 1 hour 14 parts of dimethylsulfate to the product thus obtained and stirring at a raised temperature until the reaction product dissolves in water to a clear solution a product is obtained which may be used as auxiliary agent in dyeing, for instance, as levelling and penetrative dyeing agent for vat-dyestuffs.

By treating 32.5 parts of the above amine with ethylene oxide until 100 to 200 parts are adsorbed a product is obtained which is very suitable as stripping agent.

(8) A mixture of carboxylic acids obtained by the oxidation of paraflin and containing carboxylic acids having 5 to 7 carbon atoms is transformed by way of nitriles and by hydrogenation of these nitriles into a mixture of secondary amines. 22 parts of pyridine-2,3,5,6-tetracarboxylic acid anhydride are added to 37 parts of this basic mixture and the whole is then stirred for some hours at 100 C. to 110 C. The tough brown mass is dissolved in 8 parts of caustic soda dissolved in 100 parts of water. The reaction product forms strongly foaming solutions having very good capillary active properties.

(9) 17 parts of dioctylhydroxyethylamine are dissolved in 40 parts of anhydrous ether and. 12 parts of chlorosulfom'c acid are added, drop by drop, at 0 C. to 10 C., while stirring. The whole is stirred until a test portion dissolves in dilute caustic soda solution to a clear solution, the ethe is removed by distillation and the reaction product is introduced, while cooling, at 0 C. to 10 C into dilute caustic soda solution, it being neces sary that the reaction remains always alkaline towards phenolphthalein. The reaction product has the following constitution:

The product is a very good wetting agent. We claim:

1. The process which comprises causing butyldodecylamine to react with diglycolic anhydride.

2. The product of the formula amine, di-dodecylamine and di-octodecylamine with di-glycolic acid.

4. The compounds of the following formula:

R-N-Ri 0001110 cmcoon wherein R is an alkyl radical selected from the class consisting of hexyl, iso-hexyl, ethyl-hexyl,

octyl, dodecyl. octodecyl, and R1 is an alkyl radical selected from the class consisting of hexyl, isohexyl, ethylhexyl, octyl, butyl, dodecyl and octodecyl.

LUDWIG ORTHNER.

CARL PLATZ.

HANS KELLER.

HEINZ sbNKE. 

